Bimetallic titania-based electrocatalysts deposited on ionic conductors for hydrodesulfurization reactions

ABSTRACT

This invention relates to a method for preparing a bimetallic titania-based catalyst for use in hydrodesulfurization reactions.

FIELD OF THE INVENTION

The present invention relates generally to the removal of sulfur from hydrocarbon streams and, more particularly, to a catalytic hydrodesulfurization process which allows for the in situ control of catalyst activity and selectivity.

BACKGROUND OF THE INVENTION

The passage of time has seen the enactment of ever more stringent regulations by governmental authorities based on the need to control and limit sulfur emissions from vehicle exhaust. This requires the petroleum industry to continually improve and upgrade their refinery processes to decrease the quantity of sulfur present in gasoline. Many countries around the world currently limit the allowable sulfur content to less than 50 ppm, and in some cases, as low as 20 ppm.

In many of the processes employed in the petroleum industry, hydrogen is reacted with organic hydrocarbon feedstocks in order to achieve certain desired objectives. For example, in hydrocracking it is sought to maximize the distillable fractions in oil, or its fractions. In hydrodesulfurization (HDS), the aim is the reduction of the sulfur content.

In the aforementioned processes, hydrogen is reacted with the hydrocarbon in a chemical reactor containing a catalyst. The catalyst enhances the process by increasing the reaction rate and also increasing the selectivity of the desired reaction.

Catalytic desulfurization is a preferred method for the removal of sulfur from hydrocarbons. Generally, catalytic desulfurization takes place at elevated temperature and pressure in the presence of hydrogen. At the elevated temperatures and pressures, catalytic desulfurization can result in the hydrogenation of other compounds, such as for example, olefin compounds, which may be present in the petroleum fraction which is being desulfurized. Hydrogenation of olefin products is undesirable as the olefins play an important role providing higher octane ratings (RON) of the feedstock. Thus, unintentional hydrogenation of olefin compounds during desulfurization may result in a decreased overall octane rating for the feedstock. If there is significant loss of octane rating during the hydrodesulfurization of the hydrocarbon stream, because of saturation of olefin compounds, the octane loss must be compensated for by blending substantial amounts of reformate, isomerate and alkylate into the gasoline fuel. The blending of additional compounds to increase the octane rating is typically expensive and thus detrimental to the overall economy of the refining process.

Additionally, catalytic hydrodesulfurization can result in the formation of hydrogen sulfide as a byproduct. Hydrogen sulfide produced in this manner can recombine with species present in the hydrocarbon feed, and create additional or other sulfur containing species. Olefins are one exemplary species prone to recombination with hydrogen sulfide to generate organic sulfides and thiols. This reformation to produce organic sulfides and thiols can limit the total attainable sulfur content which may be achieved by conventional catalytic desulfurization.

Alumina is a common support material used for catalyst compositions, but has several disadvantages in the desulfurization of petroleum distillates. Alumina, which is acidic, may not be well suited for the preparation of desulfurization catalysts with high loading of active catalytic species (i.e., greater than 10 weight %) for catalytically cracked gasoline. Acidic sites present on the alumina support facilitate the saturation of olefins, which in turn results in the loss of octane rating of gasoline. Additionally, recombination of the olefin with hydrogen sulfide, an inevitable result of hydrode sulfurization, produces organic sulfur compounds. Furthermore, basic species present in the feedstock, such as many nitrogen containing compounds, can bind to acidic sites on the surface of the alumina and the catalyst, thereby limiting the number of surface sites which are available for sulfur compounds for desulfurization. Furthermore, basic species present in the feedstock, such as many nitrogen containing compounds, can bind to acidic sites on the surface of the alumina and the catalyst, thereby limiting the number of surface sites which are available for sulfur compounds for desulfurization. At the same time, nitrogen containing compounds having aromatic rings are easily transformed into coke precursors, resulting in rapid coking of the catalyst. Additionally, high dispersion of the metal is difficult to enhance with an alumina support due to the strong polarity and the limited surface area of the alumina. Exemplary commercially available hydrotreating catalysts employing an alumina support include, but are not limited to, CoMo/AI₂0₃, NiMo/AI₂0₃, CoMoP/AI₂0₃, NiMoP/AI₂0₃, CoMoB/AI₂0₃, NiMoB/AI₂0₃, CoMoPBI Al₂0₃, NiMoPB/AI₂0₃, NiCoMo/AI₂0₃, NiCoMoP/AI₂0₃, NiCoMOB/AI₂0₃, and NiCoMoPB/AI₂0₃, (wherein Co is the element cobalt, Ni is nickel, Mo is molybdenum, P is phosphorous, B is boron and Al is aluminum).

In addition, prior art methods suffer in that the preparation of desulfurization catalysts having high metal loading with high dispersion is generally difficult. For example, many prior art catalysts are prepared by a conventional impregnation method wherein the catalysts are prepared by mixing the support materials with a solution that includes metal compounds, followed by filtration, drying, calcination and activation. However, catalyst particles prepared by this method are generally limited in the amount of metal which can be loaded to the support material with high dispersion, which generally does not exceed approximately 25% by weight of the metal oxide to the support material. Attempts to achieve higher loading of the metal to support materials having a relatively high surface area, such as silicon dioxide, typically result in the formation of aggregates of metallic compounds on the surface of the support. Activated carbon has much higher surface area and weaker polarity than conventional catalyst supports, such as for example, alumina and silica. This provides improved performance in the desulfurization of catalytically cracked gasoline because both olefin saturation and recombination of hydrogen sulfide with the olefin are suppressed over activated carbon support. However, weaker polarity and a relatively high hydrophobicity make activated carbon difficult to load large amount of active metallic species, such as molybdenum oxide.

It can be seen from the foregoing that methods for enhancing the performance of catalysts useful in the removal of sulfur species from petroleum-based products are needed.

SUMMARY OF THE INVENTION

The present invention provides an electrochemical catalytic method for the hydrodesulfurization of a petroleum-based hydrocarbon stream which comprises contacting the petroleum-based hydrocarbon stream with a hydrogen-containing gas in an electrochemical call employing Non Faradic Electrochemical Modification of Chemical Activity, said cell comprising an active metal catalyst working electrode applied to a charge conducting solid electrolyte, which is connected to a counter electrode, and is electrochemically promoted by applying a current or potential between the catalyst and the counter electrode during hydrodesulfurization.

The present invention also, provides a method for the preparation of a bimetallic titania-based catalyst for use in hydrodesulfurization reaction, which comprises

a) dissolving a salt of a Group VI A metal of the Periodic Table in water and adjusting the pH of the solution to an acidic value;

b) dissolving a titanic compound in the solution of step a) and adjusting the pH of the solution to an acidic value;

c) dissolving a salt of Group VIII metal of the Periodic Table in the solution of step b) and adjusting the pH of the solution to an acidic value;

d) evaporating the solution of step c) at elevated temperature and pressure and collecting a bi-metallic, titania-based solid; and,

e) calcining the bi-metallic, titania-based solid at an elevated temperature.

It has been found that in the hydroprocessing of hydrocarbon streams, the reaction rate can be enhanced, beyond the normal catalytic enhancement, by applying an electrical potential or current to the surface of the catalyst. By applying this electrical potential, the electron density on the surface of the catalyst is changed, which results in promoting or increasing the hydroprocessing reaction rate, e.g., the hydrodesulfurization (HDS) rate.

The application of an electrical potential to the surface of a catalyst is referred to as the NEMCA effect (Non-Faradic Electrochemical Modification of Catalytic Activity). The NEMCA effect is a phenomenon wherein the application of small currents and voltage potentials on catalysts in contact with solid electrolytes leads to pronounced, strongly non-Faradic and reversible changes in both catalytic activity and selectivity.

In the hydroprocessing of hydrocarbon streams, particularly hydrodesulfurization, in accordance with the present invention, the NEMCA effect is applied to good advantage. The effect is based on the discovery that by applying an electric voltage between, on the one hand, an active material which is applied, preferably in the form of layers, to a solid electrolyte and, on the other hand, a further metallic substrate, also preferably in the form of layers, which is in turn connected to a solid electrolyte, it is possible to increase the activity (rate) and selectivity of a catalyst.

Electrochemical promotion allows for in situ control of catalyst activity and selectivity by controlling in situ the promoter coverage via potential application.

In traditional catalytic processes, classical promoters are used, which typically are added during catalyst preparation, to activate a catalytic process. Another option is the use of metal-support interactions, which activates the catalytic function by using an active support. Neither of these approaches, however, provides accurate and on-demand dosage of promoters during reaction conditions.

The use of NEMCA technology allows for the precise dosing of electropromoters to a catalyst surface during reaction conditions by adjusting the flux of ions (promoters) to the catalyst surface by controlling the applied current or voltage to the cell.

Thus, in one embodiment, a method for the hydrodesulfurization of a petroleum based hydrocarbon distillate of crude oil is provided that includes the step of contacting the petroleum hydrocarbon distillate with hydrogen gas in the presence of a catalyst which has been electrochemically enhanced by the NEMCA effect.

In another embodiment, a hydrodesulfurization catalyst composition is provided whose rate of activity is enhanced by the NEMCA effect.

In still another embodiment, a method is provided for the preparation of a bi-metallic hydrodesulfurization catalyst.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts the transient effect of a constant applied negative potential (−1.5V) on the rate of H₂S formation, the conversion of thiophene and the current. T=250° C., sample: S1.

FIG. 2 depicts the transient effect of a constant applied positive (1.5V) and negative (−1.2V) potential on the rate of H₂₅ formation, the conversion of thiophene and the current. T=500° C., sample: S2.

FIG. 3 depicts the transient effect of a constant applied negative current (−1 μA) on the H₂S formation catalytic rate, the conversion of thiophene and the catalyst reference potential difference. T=300° C., sample: S3.

DETAILED DESCRIPTION OF THE INVENTION

The NEMCA effect on hydrodesulfurization catalysts can best be described as an electrochemically induced and controlled promotion effect of catalytic surfaces generated by electrolyte charge carrier spillover to/from the electrolyte onto the catalyst surface.

In one embodiment of the present invention, a catalyst composition is provided for the removal of sulfur from petroleum hydrocarbon oils. The catalyst composition is useful in the removal of sulfur from middle distillates produced at distillation temperatures ranging from 200° C. to about 450° C., for example diesel fuel.

In the hydrodesulfurization (HDS) process of the present invention, the catalyst can consist of at least one metal from the metals of Group VIII of the Periodic Table and at least one metal selected from the metals of Group VIA of the Periodic Table, which are used as the active metals to be supported on the support.

Examples of the Group VIII metals include cobalt (Co) and nickel (Ni), while examples of the Group VIA metals include molybdenum (Mo) and tungsten (W). The combination of the Group VIII metal and the Group VIA metal is preferably Mo—Co, Ni—Mo, Co—W, Ni—W, Co—Ni—Mo, or Co—Ni—W, and most preferably Mo—Co or Ni—Mo.

The content of the Group 6A metal in terms of its oxide is preferably in the range of about 1% to 30% by mass, more preferably 3% to 25%, by mass, and most preferably 5% to 20% by mass, based on the mass of the catalyst. If less than 20% by mass is employed, it would not be sufficiently active to desulfurize sufficiently, and if a mass greater than 30% were employed, it would condense resulting in reduced desulfuzation

The supporting ratio of the Group 8 metal and the Group 6A metal is a molar ratio defined by [Group 8 metal oxide]/[Group 6A metal oxide] ranging from 0.105 to 0.265, preferably 0.125 to 0.25, and most preferably from 0.15 to 0.23. A molar ratio of less than 0.105 would result in a catalyst having inadequate desulfurization activity. A molar ratio of greater than 0.265 would result in a catalyst lacking sufficient hydrogenation activity and reduced desulfurization activity.

The total content of the Group 8 metal and the Group 6A metal is preferably 22% by mass or greater, more preferably 23% by mass or greater, and most preferably 25% by mass or greater in terms of oxide based on the mass of the catalyst. A mass of less than 22% would result in a catalyst which exerts insufficient desulfurization activity.

The preferred catalyst support for use in accordance with the present invention is titanium dioxide (TiO₂). While alumina is the most widely used support material for commercial hydrodesulfurization (HDS) catalysts due to its good mechanical properties, titania based catalysts have been found to be more successful and more suitable when the HDS process is based on electrochemical promotion.

Other supports can also be employed provided they are ion conductors. Exemplary of such supports are alumina, ceria, silica, zirconia, RuO₂, CZl and BCN18.

The solid electrolyte supports which can be utilized in the process of the present invention are O²⁻ ionic conductors, exemplary of which is YSZ (8% mol Yttria Stabilized Zirconia) and low temperature (<400° C.) proton conductors, exemplary of which is BCN 18 (Ba₃CA_(1.18)Nb_(1.82)O_(9-a)).

Other solid electrolytes include β¹¹-Al₂O₃, β-Al₂O₃, Li⁺ and K⁺ conducting β-Al₂O₃.

The level of the voltage applied is usually in the range of ±0.5V to ±2V, preferably about ±1.5V.

As adverted to previously, the phenomenon of electrochemical promotion of catalysis (EPOC or NEMCA effect) has been utilized in the process of the present invention for the in situ modification of the HDS activity of bimetallic Mo—Co catalyst-electrodes at low temperatures and atmospheric pressure.

The phenomenon of electrochemical promotion of catalysis has been investigated using a variety of metal catalysts (or conductive metal oxides), solid electrolyte supports and catalytic reactions. In electrochemical promotion, the conductive catalyst-electrode is in contact with an ionic conductor and the catalyst is electrochemically promoted by applying a current or potential between the catalyst film and a counter or reference electrode, respectively. Numerous surface science and electrochemical techniques have shown that EPOC is due to electrochemically controlled migration (reverse spillover or backspillover) of promoting or poisoning ionic species (O²⁻ in the case of YSZ, TiO₂; and CeO₂, Na⁺ or K⁺ in the case of β″-Al₂O₃, protons in the case of Nafion, CZI (CaZr_(0.9)In_(0.1)O_(3-α)) and BCN18 (Ba₃Ca_(1.18)Nb_(1.82)O_(9-α)), etc.) between the ionic or mixed ionic-electronic conductor-support and the gas exposed catalyst surface, through the catalyst-gas-electrolyte three phase boundaries (TPBs).

Two parameters are commonly used to quantify the magnitude of the EPOC effect:

1. the rate enhancement ratio, ρ, defined from:

ρ=r _(o)  (1)

where r is the electropromoted catalytic rate and r_(o) the open-circuit, i.e. normal catalytic rate.

2. the apparent Faradaic efficiency, Λ, defined from:

Λ=(r−r _(o))/(I/nF)  (2)

where n is the charge of the ionic species and F the Faraday's constant.

A reaction exhibits electrochemical promotion when |Λ|>1, while electrocatalysis is limited to |Λ|≦1.

The selectivity of the reaction to the produced hydrocarbon (HC) species has been calculated by

S _(i) =r _(i) /r _(th)  (3)

where, r_(i) is the formation rate of each HC product and r_(th) the consumption rate of thiophene, equal to Σr_(i) within ±2%.

The preferred method for preparing MoCo/T₁O₂ for use in accordance with the present invention involves wet impregnation at various pH values. The wet impregnation method was used for the co-deposition of Mo and Co with a ratio of 15 wt % MoO₃ to 3 wt % CoO. The addition of 82 wt % TiO₂ (anatase) ensures a fine dispersion of the catalyst with only one monolayer of mostly Mo at the surface of the TiO₂ matrix. As indicated, wet impregnation can be carried out at different pH values. At more acidic concentrations of the solution (pH=4 or 4.3) the formation of polymeric Mo₇O₂₄ is to be expected, while at neutral conditions (pH=6.7), only monomeric MoO₄ species will be obtained.

The polymeric species (mainly [Mo₇O₂₄]⁶⁻ and [HMo₇O₂₄]⁵⁻) are deposited through electrostatic adsorption on TiO₂ surface. The monomeric species (mainly [MoO₄]²⁻) are adhered through the formation of hydrogen bonds and inner sphere complexes. Because the wet impregnation method is used to prepare the catalysts, only a small amount of the species is deposited through the above deposition modes. Thus, the greater amount of the molybdenum species is deposited through bulk deposition. This means that the species are deposited through precipitation during the water evaporation step.

Preparative Example 1 Wet Impregnation Method at pH 4.3

The preparation of the CoMo/TiO₂ (pH=4.3) catalyst is performed using the “co-impregnation under EDF conditions” method. According to this method, 0.7361 g ammonium heptamolybdate [(NH₄)₆Mo7O24*4H₂O] were dissolved in about 100 ml of triple-distilled water, in a 500 ml round flask. The pH was adjusted to 4.3 by adding concentrated HNO₃ solution dropwise. To this solution, 3.495 g of TiO2 were added and due to the Mo adsorption on TiO₂ surface and the PZC (=6.5) of the titania used, the pH rose to between 8 and 8.5. To this suspension, 0.52018 g of cobalt nitrate [Co(NO₃)2*6H₂O] were then added. Before the addition of the cobalt nitrate salt the pH was adjusted again to 4.3 in order to avoid Co(NO₃)OH precipitation. As the adsorption of cobalt species altered the solution pH to a value of 3.0-3.5, the latter had to be adjusted again to 4.3 using a concentrated ammonia solution (NH₄OH).

The round flask containing the suspension was then placed in a rotary evaporator and stirred for about 30 min. After a final adjustment to pH 4.3, the evaporation at T=40-45° C. and pressure 30 mbar was started. When the material was dried, it was transferred in a porcelain crucible and calcined at 500° C. for 2 hours in air. The final composition of the catalyst was 14.2 (10) wt % MoO₃ (Mo), 3.2 (2.6) wt % CoO (Co) and 82.6 (87.4) wt % TiO₂.

Preparative Example 2 Co-Deposited Catalyst Powder

A few drops of triple-distilled water was added to a small amount of the final powder of the wet impregnation method of Preparative Example 1 to form a thick paste, which was then spread at the surface of the proton ion conductor. The catalyst film was dried at 120° C. for 30 minutes and was then calcined at 500° C. for 2 hours.

Preparative Example 3 Procedure for Preparing Sputtered Mo Films

Thin Molybdenum (Mo) coatings are produced by a dc magnetron sputter process. By this process homogeneous, well adhered, thin metal or metal oxide coatings are produced. For the production of such coatings, suitable for electrochemical promotion, several favorable deposition parameters need to be defined.

Deposition Parameter for the Mo Catalyst-Electrodes

The sputtering parameters for the Mo coating on the CIZ electrolyte substrate with a mass of

m=0.0001 g are:

p=8.86-10.53 mTorr (˜40 ccm Ar)

P=330-403 Watt

I=0.8-1.09 Amp

V=327 Volt

Deposition Time: 10 minutes

The sputtering parameters for the Mo coating on the CIZ electrolyte substrate with a mass of

m=0.0135 g are:

p=5.57-6.74 mTorr

P=306-390 Watt

I=0.8-1.03 Amp

V=340 Volt

Deposition Time: 40 minutes

Preparative Example 4 Procedure for Preparation of MoCo Deposited on Sputtered Mo Films

A thin layer of Mo was sputtered on the CZI electrolyte and calcined at 500° C. The films were reduced in H₂ and presulfation was carried out at 500° C.

The MoCo deposited catalyst was prepared in the following way:

1. To a round bottom flask, 100 ml of triple distilled water was added.

2.3 g of (NH₄)₆Mo₇O₂₄*4H₂O was added to the 100 ml H₂O.

Preparative Example 5 Presulfation

Presulfation of the catalyst-electrolyte assembly was carried out with all catalyst-electrolyte assemblies in Examples I and II in the following manner.

-   -   A stream of Ar (20 ml/min) was passed through the reactor,         discussed in Preparative Example 8, while the reactor was heated         to 500° C. and was maintained for 30 min at 500° C.     -   A stream of 15 Vol % H₂S and 85 Vol % H₂ was supplied to the         reactor at 500° C. for 2 hours.     -   After completing the presulfation, a stream of Ar was supplied         for 1 hour at 400° C.     -   Cooling/heating to the desired reaction temperature.

Preparative Example 6

Two Different Solid Electrolyte Supports were Used:

a. YSZ (8% mol Yttria Stabilized Zirconia), an O²⁻ ionic conductor.

b. BCN18 (Ba₃Ca_(1.18)Nb_(1.82)O_(9-α)) a low temperature (<400° C.) proton conductor.

Both of the solid electrolyte pellets had a thickness of 2 mm and diameter of 18 mm.

Preparative Example 7 Preparation of Metal and Metal Oxide Interlayers

Thin Mo and TiO₂ layers were deposited over the ionic conductor supports, before the catalyst deposition, to increase the intimate contact or adhesion between the catalyst-electrode, also known as the working electrode, and the support, and to facilitate the migration of the backspillover species onto the catalyst surface. The enhancing role of TiO₂ interlayers has been reported in previous EPOC studies, both for oxidation and hydrogenation reactions.

The Mo/electrolyte and TiO₂/electrolyte type thin electrodes were prepared by metal sputtering as described previously. A magnetron sputtering system was used. High purity Ar and O₂ were used as sputtering and reactive gas, respectively. The discharge characteristics were controlled using a variable DC power supply (1 kV and 2 A). Pure Mo (99.95%) and Ti (99.95%) were used as sputtering targets.

TiO₂ thin layers were deposited only over the YSZ substrates with 600 W target power, which enabled a 0.5 nm/min deposition rate and led to a c.a. 90 nm thickness film after 3 hours of deposition. The substrate temperature was stable during the deposition at 250° C. Also, a post-deposition annealing of the deposited TiO₂ layer was performed in air at 600° C. for 60 minutes, resulting in a 60% rutile and 40% anatase structure. The TiO₂ layers structure characterization has been described previously.

Molybdenum interlayers were deposited in each case holding the target power stable at 280 W, which enabled a 20 nm/min deposition rate, achieving a 100 nm thickness Mo layer after 5 minutes of deposition. The substrate temperature was kept stable at 50° C.

On the other side of the pellets, Au counter and reference electrodes were prepared in each case by application of a metalorganic paste (Metalor, Gold resinate, A1118), followed by drying at 400° C. for 90 minutes and calcination at 650° C. for 30 minutes. Blank experiments using Au also for the working electrode showed that Au is practically catalytically inactive for the HDS reaction, establishing that the observed rate values correspond only to the rate on the catalyst-electrode and not to the counter or reference electrodes. Similar blank experiments with TiO₂ powder showed that TiO₂ also is inactive under the mentioned conditions.

Preparative Example 8 Reactor Operation

An atmospheric pressure electrochemically promoted single chamber reactor was used equipped with a solid electrolyte pellet, on which three electrodes were deposited, namely, the working-catalyst electrode, the counter electrode and the reference electrode. Gold wires were used for the electrical connections between the electrocatalytic element and the external power supply unit. A three-bore, ultra high vacuum feed-through unit, special for high temperature H₂ and H₂S environment, was used for the gastight introduction of the gold wires in the reactor. The temperature was measured and controlled by a type-K thermocouple placed in a stainless steel close-end tube in the proximity of the catalyst electrode.

The feed gas composition and total gas flow rate, F_(T), was controlled by four mass flowmeters (Brooks smart mass flow and controller, B5878). Reactants were Messer-Griesheim certified standards of pure (99.99%) H₂ and H₂S, while thiophene was introduced using a saturator (P_(th) ^(25° C.)=3 kPa) with Ar or H₂ carrier gas. Pure (99.99%) argon was fed through the fourth flowmeter in order to further adjust total gas flow rate and inlet gas composition at desired levels. H₂ partial pressure was held constant at 97 kPa, while thiophene partial pressure could be varied from 0.5 to 5 kPa. The total gas flow rate was constant at 30 and 60 cm³/min. Reactants and products were analyzed by on-line gas chromatography (Shimadzu 10A, equipped with a Porapaq-QS column at 50° C. for the separation of thiophene and the produced C_(x)H_(y)) in conjunction with a continuous analysis H₂S colorimeter (Applied Analytics Inc.). Constant currents or potentials were applied using an AMEL 2053 galvanostat-potentiostat.

TABLE 1 Electrochemical Cells Used in Examples Counter/ Working Reference Sample Cell Electrode Interlayer Electrolyte Electrode S1 MoCo/TiO₂/YSZ/Au MoCo TiO₂ YSZ Au (impregnation) (sputtering) S2 MoCo—TiO₂/ MoCo/TiO₂ Mo YSZ Au Mo/YSZ/Au (dispersed- (sputtering) impregnation) S3 MoCo—TiO₂/ MoCo/TiO₂ Mo BCN18 Au Mo/BCN18/Au (dispersed- (sputtering) impregnation)

Example I The Use of O²⁻ Ionic Conductor Support (YSZ)

As can be seen by an examination of FIG. 1, it shows the transient effect of a constant applied negative potential (−1.5V) on the rate of H₂S formation (reaction (4)), the conversion of thiophene and the current at 250° C., using sample S1, i.e. Mo—Co/TiO₂(sp)/YSZ/Au, identified more fully in Table 1 and the preparative examples.

C ₄ H ₄ S+H ₂ →C _(x) H _(y) +H ₂ S  (4)

As shown, under open circuit, i.e. normal catalytic conditions, the conversion of thiophene is ˜0.5%. Negative potential application (−1.5V) causes a 3.9-fold increase of the catalytic rate (ρ=3.9), where thiophene conversion reaches ˜2%, while the apparent Faradaic efficiency is 0.2. However, in the present instance where oxygen is not present in the gas mixture, any current or potential-induced catalytic rate change suggests electrochemical promotion, even when |Λ|<1. On the other hand, positive potential application has no effect on the catalytic rate. The electrophilic behavior observed here, i.e. rate increase by electrode potential or work function decrease, appears when the electron acceptor (i.e. thiophene) species is weakly adsorbed on the catalytic surface and the electron donor (H₂) strongly adsorbed. This agrees with the positive order dependence of the reaction rate on P_(th), proposed in the literature. Upon the application of negative potential, i.e. O²⁻ pumping from the catalytic electrode, the thiophene-catalyst bond strength increases and causes higher thiophene coverage of the catalytic surface.

After current interruption the catalytic rate reversibly returns to its initial open-circuit steady-state value. This indicates that the surface sulfur species, formed during the sulfation pretreatment step, were not consumed upon negative polarization, which would cause catalyst partial deactivation.

As can be seen by an examination of FIG. 2, it shows the transient effect of a constant applied positive (1.5V) and negative (−1.2V) potential on the rate of H₂S formation (reaction (4) above), the conversion of thiophene and the current at 500° C., using sample S2 identified more fully in Table 1 and the preparative examples, where the CoMo—TiO₂ dispersed catalyst coating is supported over a thin sputter deposited Mo film interfaced with YSZ.

As shown, under open-circuit conditions the conversion of thiophene is ˜0.7%, similar to that obtained using sample S1 (FIG. 1) at 250° C. Positive potential application (1.5V) causes an 1.5-fold increase of the catalytic rate, while the apparent Faradaic efficiency is 0.1. This is in contrast to the behavior of sample S1, where positive polarization had no effect on the rate. On the other hand, application of a negative potential (−1.2V) causes a similar less pronounced effect on the rate where ρ=1.5, indicating the inverted volcano behaviour of the system. This change from electrophilic to inverted volcano behavior, utilizing similar samples (S1 and S2), S2 is mainly due to the high operating temperature for sample S2. At elevated temperatures both electron acceptor and electron donor species are weakly bonded on the catalytic surface, which results in the observed inverted volcano behavior of FIG. 2. Similar change of the EPOC behaviour by temperature increase has been reported in previous studies on the model reaction of C₂H₄ oxidation over Pt/YSZ, where the behaviour changes from electrophobic to inverted volcano.

After positive current interruption, the catalytic rate decreases to a value lower (?) than the initial open-circuit steady-state value, indicating a deactivation of the catalyst.

Example II The Use of Proton Conductor Support (BCN18)

As can be seen by an examination of FIG. 3, it shows the transient effect of a constant applied negative current (−1 μA) on the H₂S formation catalytic rate, the conversion of thiophene and the catalyst electrode-reference potential difference at 300° C. using sample S3, identified more fully in Table 1 and the preparative examples.

As shown, negative current application causes a 10% increase of the catalytic rate (ρ=1.1), while the apparent Faradaic efficiency equals 585, i.e. each proton present on the catalyst surface, which establishes an effective double layer, causes the reaction of up to 585 adsorbed from the gas phase hydrogen species. After the negative current interruption, the catalytic rate decreases and stabilizes at a value lower than the initial value. This “poisoning” effect of the negative polarization can be attributed to possible hydrogenation of the catalytically active surface sulfur groups supplied by the backspillover proton species upon negative polarization.

While certain representative embodiments and details have been shown for purposes of illustrating the invention, it will be apparent to those skilled in the art that various changes in the methods and the electrochemical cell disclosed herein may be made without departing from the scope of the invention, which is defined in the appended claims. 

1. A method for the preparation of a bimetallic titania-based catalyst for use in hydrodesulfurization reactions, which comprises the steps of: a) dissolving a salt of a Group VI A metal of the Periodic Table in water and adjusting the pH of the solution to an acidic value; b) dissolving a titania compound in the solution of step a) and adjusting the pH of the solution to an acidic value; c) dissolving a salt of a Group VIII metal of the Periodic Table in the solution of step b) and adjusting the pH of the solution to an acidic value; d) evaporating the solution of step c) at elevated temperature and pressure and collecting a bi-metallic, titania-based solid; and e) calcining the bi-metallic titania-based solid at an elevated temperature.
 2. The method of claim 1, wherein the solution pH is adjusted to about 4.3 in step a).
 3. The method of claim 1, wherein the solution pH is adjusted to about 4.3 in step b).
 4. The method of claim 1, wherein the solution pH is adjusted to about 4.3 in step c).
 5. The method of claim 1, wherein the Group VIA metal is molybdenum or tungsten.
 6. The method of claim 5, wherein the Group VIA metal is molybdenum.
 7. The method of claim 1, wherein the Group VIA metal salt is (NH₄)₆Mo₇O₂₄*4H₂0.
 8. The method of claim 1, wherein the Group VIII metal is cobalt or nickel.
 9. The method of claim 8, wherein the Group VIII metal is cobalt.
 10. The method of claim 1, wherein the Group VIII metal salt is Co(NO₃)₂*6H₂0.
 11. The method of claim 1, and including the deposition of the bi-metallic titania-based catalyst on an ionic solid electrolyte support.
 12. The method of claim 11, wherein the ionic solid electrolyte support is a proton conducting solid electrolyte or an oxygen ion solid electrolyte.
 13. The method of claim 12, wherein the proton conducting solid electrolyte is BCN18 or CZI and the oxygen ion solid electrolyte is YSZ.
 14. The method of claim 11 and including the deposition of an intermediate layer of TiO₂ or Mo on the ionic solid electrolyte support to increase the adhesion between the support and the catalyst.
 15. The method of claim 14, wherein the TiO₂ or Mo intermediate layers are applied to the support by metal sputtering.
 16. A method of preparing a CoMo/TiO₂ catalyst using co-impregnation under Equilibrium Deposition Filtration (EDF), which comprises the steps of: a) dissolving a molybdenum salt in water and adjusting the pH of the solution to an acid value; b) dissolving a titania compound in the solution of step a) and adjusting the pH of the solution to an acid value; c) dissolving a cobalt salt in the solution of step b) and adjusting the pH of the solution to an acid value; d) evaporating the solution of step c) at elevated temperature and press and collecting a CoMo/TiO₂ solid; and e) calcing the CoMo/TiO₂ at elevated temperature
 17. The method according to claim 16, wherein the pH in step a) is adjusted to 4.3.
 18. The method according to claim 17, wherein the pH of the solution in step a) is adjusted with HNO₃.
 19. The method according to claim 16, wherein the pH in step b) is adjusted to 4.3.
 20. The method according to claim 19, wherein the pH of the solution in step b) is adjusted to 4.3.
 21. The method according to claim 16, wherein the evaporation in step e) is conducted at a temperature of about 40° C. to about 45° C. and at a pressure of 30 mbar.
 22. The method according to claim 16, wherein the calcinations in step e) is conducted at about 500° C. for about 2 hours.
 23. The method according to claim 16, wherein the final composition of the catalyst is about 14.2 (10) wt. % MoO₃ (Mo), 3.2 (2.6) wt. % CoO (Co) and 82.6 (87.4) wt. % TiO₂.
 24. An electrochemical cell for the hydrodesulfurization of a hydrocarbon stream or distilled fractions thereof, which comprises: a titania-based active catalyst electrode which includes at least one Group VI A metal and at least one Group VIII metal of the Periodic Table supported on an ionic charge conducting solid electrolyte, said catalyst electrode being in intimate contact with said solid electrolyte which is in intimate contact with a counter electrode, whereby when an electric current is applied, it flows through the ionic conducting solid electrolyte to maintain the titania-based active catalyst at a constant potential and a voltage is applied to the catalyst during hydrodesulfurization to promote the reaction rate.
 25. The electrochemical cell of claim 24, wherein the Group VIA metal is selected from molybdenum or tungsten.
 26. The electrochemical cell of claim 25, wherein the metal is molybdenum.
 27. The electrochemical cell of claim 24, wherein the Group VIII metal is cobalt or nickel.
 28. The electrochemical cell of claim 27, wherein the metal is cobalt.
 29. The electrochemical cell of claim 24, wherein the charge conducting solid electrolyte support is a proton conducting solid electrolyte or an oxygen ion solid electrolyte.
 30. The electrochemical cell of claim 29, wherein the proton conducting solid electrolyte support is BCN18 or CZI and the oxygen ionic solid electrolyte support is YSZ.
 31. The electrochemical cell of claim 24, and including an intermediate layer of TiO₂ or Mo between the ionic solid electrolyte support and the catalyst to increase adhesion between the support and the catalyst is increased.
 32. The electrochemical cell of claim 30, wherein the intermediate layer is applied by metal sputtering. 